WO2006061993A1 - 膜電極複合体およびその製造方法、ならびに燃料電池 - Google Patents
膜電極複合体およびその製造方法、ならびに燃料電池 Download PDFInfo
- Publication number
- WO2006061993A1 WO2006061993A1 PCT/JP2005/021507 JP2005021507W WO2006061993A1 WO 2006061993 A1 WO2006061993 A1 WO 2006061993A1 JP 2005021507 W JP2005021507 W JP 2005021507W WO 2006061993 A1 WO2006061993 A1 WO 2006061993A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electrolyte membrane
- membrane
- reducing composition
- electrode assembly
- electrode
- Prior art date
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0297—Arrangements for joining electrodes, reservoir layers, heat exchange units or bipolar separators to each other
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04197—Preventing means for fuel crossover
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1053—Polymer electrolyte composites, mixtures or blends consisting of layers of polymers with at least one layer being ionically conductive
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0094—Composites in the form of layered products, e.g. coatings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
- Y10T156/1089—Methods of surface bonding and/or assembly therefor of discrete laminae to single face of additional lamina
- Y10T156/1092—All laminae planar and face to face
Definitions
- the present invention relates to a membrane electrode composite capable of achieving a high power density and a method for producing the same
- a fuel cell is a power generation device that has low emissions and high energy efficiency and has a low burden on the environment. For this reason, it is in the spotlight again in recent years due to the rise in global environmental protection.
- this power generation device is expected in the future as a relatively small-scale distributed generation facility, and as a power generation device for mobile objects such as automobiles and ships. It is also attracting attention as a power source for small mobile devices and portable devices, as an alternative to secondary batteries such as nickel metal hydride batteries and lithium ion batteries, as a charger for secondary batteries, and as a secondary battery.
- the combined use (hybrid) is expected to be installed in mobile devices such as mobile phones.
- PEFC Polymer Electrolyte Fuel Cells
- Direct fuel cells that directly supply fuel such as methanol are also attracting attention.
- direct fuel cells have a lower output than conventional PEFCs, the fuel is liquid and does not use a reformer, so the energy density is high and the usage time of portable devices per filling is long. There is an advantage.
- a polymer electrolyte fuel cell is composed of an anode and a force sword electrode in which a reaction responsible for power generation occurs, and a polymer electrolyte membrane serving as a proton conductor between the anode and the force sword.
- the body (MEA) is composed of cells that are sandwiched by separators.
- the electrode is composed of an electrode substrate (also called a gas diffusion electrode or a current collector) that promotes gas diffusion and collects (supply) electricity, and a catalyst layer and force that actually becomes an electrochemical reaction field. Yes.
- the anode electrode fuel such as hydrogen gas reacts with the catalyst layer of the anode electrode to produce protons and electrons, which are conducted to the electrode substrate, Ton conducts to the polymer electrolyte membrane.
- the anode electrode is required to have good gas diffusivity, electron conductivity, and proton conductivity.
- oxygen and oxygen or other oxidizing gas is a catalyst layer of the force sword electrode, and protons conducted from the polymer electrolyte membrane react with electrons conducted from the electrode substrate to react with water. Is generated. For this reason, in the force sword electrode, it is necessary to efficiently discharge generated water in addition to gas diffusibility, electron conductivity, and proton conductivity.
- direct fuel cells using methanol or the like as fuel are required to have different performance from conventional PEFCs using hydrogen gas as fuel. That is, in a direct fuel cell, at the anode electrode, a fuel such as a methanol aqueous solution reacts with the catalyst layer of the anode electrode to produce protons, electrons, and carbon dioxide. Mouth tons are conducted to the polymer electrolyte, and carbon dioxide is released from the system through the electrode substrate. For this reason, in addition to the required characteristics of the anode electrode of the conventional PEFC, fuel permeability such as aqueous methanol solution and carbon dioxide emission are also required.
- fuel permeability such as aqueous methanol solution and carbon dioxide emission are also required.
- JP-A-4-132168 a method in which a perfluorinated proton conductive polymer is applied to an electrode and dried, and then the electrode and the membrane are integrated by a high-temperature press, sodium styrenesulfonate and hexaethylene glycol as a crosslinking agent are disclosed. Illustrated is a method in which a monomer composition solution such as dimetatalate is applied to an electrode, joined to an electrolyte membrane, heated and pressurized for 1 hour or longer, and the membrane and the electrode are integrated via a crosslinked polymer of the monomer. Yes.
- the present invention in particular, maintains an effect of suppressing fuel crossover even in an electrolyte membrane having high heat resistance, high strength, high tensile elastic modulus and low water content, and in a short time,
- the present invention provides a method for producing a membrane electrode composite that can easily reduce the resistance at the interface between the electrode and the electrolyte membrane at a low temperature and a low pressure, and further provides a high-power density fuel cell.
- the present invention also provides a membrane electrode assembly that can take out a high output density with a high fuel crossover suppression effect using an electrolyte membrane having high heat resistance, high strength, high tensile modulus, and low water content. In addition, they are trying to provide high-power fuel cells that use them.
- the present invention employs the following means. That is, the present invention relates to a method for producing a membrane electrode composite comprising an electrolyte membrane between a pair of electrodes, wherein at least one of the electrodes is composed of a polymer material having an ionic group and a plasticizer. Bonding to the electrolyte membrane through the interfacial resistance reducing composition (including bonding the electrode and the electrolyte membrane, and integrating them after bonding the electrode and the electrolyte membrane) A membrane electrode assembly having a step and a step of removing part or all of the plasticizer from the interface resistance-reducing composition by extraction with a solvent. It is a manufacturing method.
- the present invention provides a membrane electrode composite comprising an electrolyte membrane interposed between a pair of electrodes, and has a layer (A) between at least one electrode and the electrolyte membrane, and is measured with an ultra-micro hardness meter
- the storage elastic modulus of the electrolyte membrane is C
- the value of the storage elastic modulus C is 1 GPa or more.
- the present invention provides a membrane electrode composite comprising an electrolyte membrane between a pair of electrodes, A fragrance having a layer (A) whose phase difference measured by tapping mode scanning with a scanning probe microscope is different from that of the electrolyte membrane, and the electrolyte membrane and the layer (A) have an anionic group between at least one electrode and the electrolyte membrane. It is a membrane electrode composite containing a group hydrocarbon.
- the fuel cell of the present invention is characterized by using the membrane electrode assembly.
- the present invention even when an electrolyte membrane having high heat resistance, high strength, high tensile elastic modulus and low water content is used, low interface resistance between the electrode of the membrane electrode composite and the electrolyte membrane can be achieved. Thus, it is possible to provide a high power density fuel cell by using a powerful membrane electrode assembly. Further, according to the present invention, a membrane electrode assembly having low fuel crossover property, high output density and high durability can be provided, and a high output fuel cell can be provided by using such a membrane electrode assembly. It becomes possible to do.
- Fig. 1 is an example of circular fitting of impedance measurement results of a membrane electrode assembly.
- FIG. 2 is a voltage-current characteristic diagram of a fuel cell using the membrane electrode assembly of Example 1 and Comparative Example 1 of the present invention.
- FIG. 5 is a graph showing the relationship between the ratio of the output of a fuel cell using the interface resistance reducing composition and the output of a fuel cell without using the interface resistance reducing composition.
- FIG. 4 is a diagram showing an example of a stacked fuel cell.
- FIG. 7 is a cross-sectional view of an example of a passive fuel cell.
- FIG. 8 is a graph showing the temperature dependence of the viscosity change of the interface resistance-reducing composition B in Example 2.
- the method for producing a membrane electrode composite of the present invention comprises a membrane electrode composite comprising an electrolyte membrane interposed between a pair of electrodes, wherein at least one electrode is formed of an interface resistance reducing composition containing a plasticizer. It is essential to have a step of attaching to the electrolyte membrane.
- tensile modulus of lOOMPa or higher in order to suppress fuel membrane crossover in the electrolyte membrane and to improve mechanical strength, high heat resistance with a glass transition point of 120 ° C or higher due to dynamic viscoelasticity, tensile modulus of lOOMPa or higher, preferably Preferably has a high elastic modulus of 500 MPa or higher, more preferably lOOOMPa or higher, and a molecular structure that can obtain a low moisture content of 100% or lower with respect to the weight of the electrolyte membrane. Tend to be.
- interposing an interfacial resistance reducing composition containing a plasticizer when the electrode and the electrolyte membrane are combined at least a part of the fine gap between the electrode and the electrolyte membrane is filled with the interfacial resistance reducing composition.
- the substantial contact area can be increased, and the increase in resistance due to the entry of fuel and air used as a fuel cell, water, and carbon dioxide into the air gap can be prevented.
- the interface resistance reducing composition penetrates into the cracks generated in the catalyst layer of the electrode, and the inner wall surface of the cracked catalyst layer crack that cannot be used for conventional power generation can be used effectively.
- the contact area of the catalyst can be increased.
- the resistance of the membrane electrode assembly decreases, the power density increases, and a high-performance fuel cell can be obtained.
- the electrolyte membrane has pinholes, surface defects, etc., it can be protected and repaired by a layer made of the interface resistance reducing composition, and the performance as a membrane electrode composite can be stabilized. It is possible to improve durability.
- the low interface resistance it is preferable for the low interface resistance that 50% or more of the area (projected area) of at least one of the electrodes is combined with the electrolyte membrane through the interface resistance reducing composition. More preferably 75% or more, more preferably 95% or more. Furthermore, the area of each pair of electrodes is 50% or more combined with the electrolyte membrane via the interfacial resistance reducing composition. More preferably, 75% or more is more preferable, and 95% or more is most preferable. .
- the composition for reducing interfacial resistance of the present invention has ionic conductivity, can be fluidized or plastically deformed at least when the electrode and the electrolyte membrane are combined, and fills voids in the electrode so that fuel and It does not inhibit the diffusion of air, generated water and carbon dioxide, has good adhesion to the electrolyte membrane, does not adversely affect the catalyst performance, and does not flow at least during power generation as a membrane electrode composite, That is, it is preferable that the fuel does not swell excessively and does not dissolve, for example, when methanol aqueous solution is methanol, the fuel satisfies the conditions such as methanol resistance and strength equal to or higher than the electrolyte membrane to be used. As a result of intensive studies that satisfy these conditions, the inventors have found that the following compositions are preferable.
- the interface resistance-reducing composition used in the present invention must contain a polymer material having an ionic group.
- ionic groups are preferably those having a proton exchange capacity that is favorably favored by negatively charged atomic groups.
- functional groups include sulfonic acid groups (one SO (03 ⁇ 4), sulfate group (-030 (OH)),
- Ruphonimide group (—SO NHSO R (R represents an organic group;)
- phosphonic acid group (—PO (OH)
- Two or more kinds of these ionic groups can be contained in the polymer material, and may be preferable by combining them.
- the combination is appropriately determined depending on the structure of the polymer. Among them, it is more preferable to have at least one of a sulfonic acid group, a sulfonimide group, and a sulfuric acid group from the viewpoint of high proton conductivity. In terms of hydrolysis resistance, it is most preferable to have at least a sulfonic acid group. I like it.
- the density of the sulfonic acid group is preferably 0.1 to 5.
- OmmolZg more preferably 0.5 to 3.5 mmol from the viewpoint of proton conductivity and fuel crossover suppression. More preferably, it is 1.0 to 3.5 mmol Zg.
- ionic conductivity that is, low interface resistance can be maintained. 5.
- a liquid fuel such as a direct methanol fuel cell can be used. When used in a fuel cell that is in direct contact, the interface resistance reducing layer can be prevented from being excessively swollen by the fuel and leaching out or flowing out.
- the sulfonic acid group density is the molar amount of sulfonic acid groups introduced per unit dry weight of the polymer material, and this value is larger! /, The degree of sulfonation! /, Is high!
- the sulfonic acid group density of the polymer material used can be measured by elemental analysis, neutralization titration or nuclear magnetic resonance spectroscopy. Elemental analysis is preferred because of the ease and accuracy of sulfonic acid group density measurement.
- the neutralization titration method should be used when it is difficult to calculate the exact sulfonic acid group density by elemental analysis, such as when a sulfur source is included in addition to the sulfonic acid group.
- the polymer material having an ionic group include a polymer electrolyte having an aromatic ring in the main chain from the viewpoint of mechanical strength, fuel durability, heat resistance, and the like of the interface resistance-reducing layer.
- polyether ketone and ionic group-containing polyether ether ketone are preferably used.
- the ionic group is as described above.
- an ionic group may be introduced into the polymer, or a monomer having an ionic group may be polymerized. Introduction of phosphonic acid groups into the polymer can be performed by the method described in “Polymer Preprints Japan”, 51, 750 (2002).
- Introduction of phosphate groups into the polymer can be achieved, for example, by phosphate esters of polymers having hydroxyl groups.
- Introduction of a carboxylic acid group into the polymer can be performed by, for example, acidifying a polymer having an alkyl group or a hydroxyalkyl group.
- Introduction of a sulfonimide group into the polymer can be achieved by, for example, treating a polymer having a sulfonic acid group with an alkylsulfonamide.
- the introduction of a sulfate group into the polymer is possible, for example, by sulfate ester of a polymer having a hydroxyl group.
- Introduction of sulfonic acid groups into the polymer can be carried out, for example, by a method in which the polymer is reacted with chlorosulfonic acid, concentrated sulfuric acid or fuming sulfuric acid.
- ionic group introduction methods can be controlled to a target ionic group density by appropriately selecting conditions such as treatment time, concentration, and temperature.
- the weight average molecular weight is preferably 10,000 to 5,000,000, more preferably 30,000 to 1,000,000.
- the weight average molecular weight is preferably 10,000 to 5,000,000, more preferably 30,000 to 1,000,000.
- the interface resistance reducing composition used in the present invention must contain a plasticizer.
- a plasticizer that satisfies the above-described conditions for the interfacial resistance reducing composition is selected.
- the reason why it is necessary to include a plasticizer is that the interface resistance-reducing composition is below the decomposition temperature of the polymer material having the ionic group and below the temperature at which no adverse effects such as decomposition and deformation of the material used occur. The point that makes it possible to flow Can be mentioned.
- a plasticizer is not included, it is necessary to raise the temperature above the softening point of the polymer electrolyte, which adversely affects other materials used. Therefore, the performance as a membrane electrode composite may be insufficient.
- plasticizers those that have hydrogen bonding properties with the ionic groups of the aromatic hydrocarbon polymer having the ionic group and whose number of hydrogen bonds can be changed depending on the temperature, that is, a composition having a low interface resistance.
- ethylene glycol and propylene glycol are preferred.
- Polyhydric alcohols such as trimethylene glycol and glycerin are preferably used.
- the plasticizer is at least partially or after the electrode and the electrolyte membrane are bonded or the electrode catalyst layer.
- it is preferable to remove by extraction with water or a solvent containing water. Therefore, a water-soluble plasticizer is particularly preferable.
- it is excellent in compatibility with a polymer material having an ion group having an aromatic ring in the main chain, can maintain a shape at room temperature, and provides an interface resistance reducing composition with good hot melt properties. Low volatility! More preferred are polyhydric alcohols which are particularly preferred.
- the selected plasticizer or solvent immediately affects the electrolyte membrane.
- the effect of reducing the fuel crossover is reduced, or the strength is lowered and the durability is affected.
- the performance of the membrane electrode assembly is affected, such as when a part of the plasticizer or the solvent is provided on the electrode with at least an interfacial resistance reducing composition, before the electrode and the electrolyte membrane are bonded together Extraction removal with water or a solvent containing water that is preferably removed Is preferred.
- the interfacial resistance reducing composition is provided on the electrode, only a part of the plasticizer is removed before the electrode and the electrolyte membrane are bonded together. If the agent is not present, the adhesion between the interface resistance reducing composition provided on the electrode and the electrolyte membrane and the unevenness of the electrode catalyst layer are reduced, and the durability and output of the membrane electrode composite are improved. This is because the effects of the invention cannot be obtained.
- the plasticizer in the present invention has good storage stability as an interfacial resistance reducing composition that hardly volatilizes when using the interfacial resistance reducing composition. From the viewpoint of this, it is preferable.
- a plasticizer suitable for the present invention a thermogravimetric analysis of a sample after processing the interface resistance reducing composition into a sheet of 100 to 200 ⁇ m and drying in hot air at 100 ° C. for 1 hour ( TG—DTA), and the thermal weight loss rate between 100 ° C and 300 ° C (temperature increase rate 10 ° CZ min, under N atmosphere) is in the range of 5% to 90%, or at room temperature
- an interfacial resistance reducing composition that falls within the range of 5% to 90% of weight loss before immersion. Things are preferred. If the weight loss rate in these measurement methods is 5% or more, it can have fluidity and plastic deformability when the electrolyte membrane and the electrode are combined, and an excellent performance membrane electrode assembly can be obtained. it can. On the other hand, if it is 90% or less, the possibility that the voids in the electrode are filled with the interface resistance reducing composition is reduced, and a membrane electrode composite having excellent performance can be obtained. Further, the storage stability is improved, which is preferable from the viewpoint of cost. More preferably, it is 10% or more and 85% or less, and further preferably 20% or more and 80% or less.
- the amount is too large, it penetrates into the electrolyte membrane and tends to decrease the fuel barrier property of the electrolyte membrane or short-circuit the membrane electrode assembly.
- this component 1% by weight or more and 70% by weight or less in the composition for reducing interface resistance is preferred, and 2% by weight or more and 50% by weight or less are more preferred.
- a method for producing the interface resistance-reducing composition generally known methods can be selected.
- a polymer material having a ionic group, its solvent, and a plasticizer can be put into a suitable container and stirred.
- examples thereof include a method of kneading at a temperature and a method of melting and kneading a polymer material having an ionic group and a plasticizer in an extruder or a kneader. At this time, it may be heated as necessary.
- the solvent selected is preferably a solvent that can dissolve 10% by weight or more of a polymer material having an ionic group and can be uniformly mixed with a plasticizer.
- a solvent that can dissolve 10% by weight or more of a polymer material having an ionic group and can be uniformly mixed with a plasticizer.
- Protic polar solvents such as ⁇ -petit latatotone and butyl acetate, carbonate solvents such as ethylene carbonate and propylene carbonate, ethylene glycol monomethyl ether, ethylene glycol monoethyl etherate, propylene glycol monomethinole Alkylene glycol monoalkyl ethers such as etherol and propylene glycol monoethyl ether, and alcohol solvents such as isopropanol V- are preferably used.
- the polymer electrode in addition to the polymer material and the plasticizer having the ionic group, is used for the purpose of improving the strength, adhesion, fuel resistance, etc. of the low interface resistance layer.
- Various inorganic fillers such as montmorillonite glass fiber, carbon materials such as carbon fiber and carbon nanotubes, silica, alumina, zirconia, titania Various fines such as polysilsesquioxane Even if the particulate matter is added, the function of the interface resistance reducing composition is not adversely affected.
- the ratio of the polymer material having an ionic group and the plasticizer in the composition for reducing interface resistance is preferably 10% by weight or more, more preferably 30% by weight or more. Preferably it is 40 weight% or more.
- a film composed of the interface resistance reducing composition alone is laminated and bonded between the electrode and the electrolyte film, and the interface resistance reducing composition is injected into the gap while keeping the electrode and the electrolyte film at a predetermined interval in advance.
- An example of such a process is as follows.
- a process of providing and bonding an interfacial resistance reducing composition on an electrode and Z or an electrolyte membrane is preferable.
- the method for providing the interface resistance reducing composition on the electrode or the electrolyte membrane include a method in which the composition is applied directly on the electrode catalyst surface or the electrolyte membrane, or the interface resistance reducing composition is applied to another substrate. Examples include a method of removing the base material by pasting it with an electrode or an electrolyte membrane after coating.
- interfacial resistance reducing composition As an application method of the interfacial resistance reducing composition, generally known methods can be used. Techniques such as spray coating, brush coating, dip coating, slit die coating, curtain coating, flow coating, spin coating, screen printing, etc. Is applicable. In addition, when the interface resistance reducing composition cannot be applied at room temperature, a hot melt coating method in which the composition is heated and melted and then coated by the above method and then cooled can be applied. In addition, after the interfacial resistance reducing composition is provided on the electrode or the electrolyte membrane, it is pasted together so that the interfacial resistance reducing composition does not flow.
- a solvent used to dissolve a plasticizer or a polymer material having an ionic group, it should not be adversely affected on the electrode or the electrolyte membrane.
- a part of the plasticizer and solvent in the interface resistance reducing composition can be dried and adjusted.
- the viscosity of the interfacial resistance reducing composition used in the present invention is preferably such that the viscosity decreases as the temperature becomes higher than the room temperature, such as during pressing or coating, for example, having an ionic group.
- Viscosity at 30 ° C measured at a shear rate of 35 (s _1 ) using a rotary viscometer with a polymer material, a plasticizer, and optionally a solvent, at X (Pa), 80 ° C YZX is preferably 0.3 or less, where Y (Pa) is the viscosity.
- YZ X obtained by measuring in this way shows the temperature dependence of the viscosity of the interface resistance reducing composition, and the smaller the value, the more the temperature range that can be adopted for production of 30 ° C to 80 ° C. Since the viscosity change is large, if YZX is 0.3 or less, it is easy to handle at room temperature at the time of manufacturing the membrane electrode assembly at room temperature. At the time of heating press or hot-met coating at room temperature or higher, the fluidity of the interfacial resistance-reducing composition is increased (viscosity is decreased), and the followability of the catalyst layer can be increased, and as a membrane electrode composite The viewpoint power of high output is also preferable. 0.2 or less is more preferable 0.1 or less is more preferable.
- the viscosity X value at 30 ° C is preferably 50 Pa or more, more preferably 70 Pa, more preferably lOOPa or more, and even more difficult measurement conditions.
- the viscosity Y value at 80 ° C is as small as possible, and the viewpoint power of catalyst layer followability is also preferred.
- Such an interfacial resistance-reducing composition can be produced as follows. For example, a polymer material having an ionic group is dissolved in a solvent capable of dissolving 10% by weight or more of an ionic group and can be uniformly mixed with a plasticizer. Added .
- a plasticizer is a poor solvent that cannot dissolve a polymer material having an ionic group. Therefore, it is difficult to obtain a uniform interface resistance-reducing composition by depositing a polymer material having an ionic group. .
- a polymer material having such an ionic group and a plasticizer a polymer material having a sulfonic acid group or a derivative thereof as an ionic group and a plasticizer having a hydroxyl group, an amide group, a carboxyl group, etc.
- a combination of polyhydric alcohols such as glycerin is preferred as a plasticizer from the viewpoint of storage stability and workability.
- YZX is preferably determined as appropriate experimentally depending on the method of coating the interface resistance reducing composition, the manufacturing conditions of the membrane electrode assembly, etc., but this control is performed on the polymer material having an ionic group. This is possible depending on the type, ionic group density, type and addition amount of plasticizer, addition amount of solvent, etc.
- the composition of the interfacial resistance reducing composition can be experimentally changed appropriately according to the selected material and production conditions. it can.
- the solvent here may be allowed to remain in the interface resistance reducing composition for easy mixing of the polymer material having an ionic group and the plasticizer and for adjusting YZX.
- YZX can be adjusted under conditions where it can be removed by drying or the like before it is used as a composition for reducing interfacial resistance in the production of a membrane electrode assembly.
- a polymer material having an ionic group and a plasticizer are mechanically mixed with a kneading machine or a kneader at a temperature lower than the decomposition temperature or boiling point of the plasticizer. It is also possible to form the sheet-like interfacial resistance-reducing composition and use it.
- the viscosity change of the interfacial resistance-reducing composition is reversible until the plasticizer is removed.
- the interfacial resistance-reducing composition is applied to a release paper or the electrode, the interfacial resistance is reduced.
- the product directly coated with the conductive composition can be stored after being cooled to room temperature, and the time constraints during the production of the membrane electrode composite can be alleviated.
- the coating amount of the surface resistance reducing composition 0. 5mgZcm 2 or more as a composition, preferably 30mgZc m 2 or less.
- 0.5 mgZcm 2 or more the gap between the electrode and the electrolyte membrane and the catalyst layer crack can be filled, and a low interface resistance can be achieved.
- it is 30 mgZcm 2 or less, the possibility of filling gaps necessary for the diffusion of fuel and generated gas other than the gap between the electrode and the electrolyte membrane is reduced, and the plasticizer contained in the interface resistance reducing composition Reduced adverse effects Is done. It is more preferably lmgZcm 2 or more and lOmgZcm 2 or less.
- the electrode and the electrolyte membrane can be combined by a generally known method (for example, the chemical plating method described in "Electrochemistry” 1985, 53, 269, “Jelect Elect Mole Chemical Science” (J. Electrochem. Soc.)). : Gas diffusion electrode heating press bonding method described in Electrochemical Science and Technology, 1988, 135 (9), 2209.
- the integration by heating press is a preferable method, but the temperature and pressure may be appropriately selected depending on the thickness of the electrolyte membrane, the moisture content, the catalyst layer and the electrode substrate.
- the composite film can be formed by pressing even when the electrolyte membrane is dried or absorbed.
- the electrolyte membrane in the method of the present invention, normally, if the electrolyte membrane is not in a water-containing state, it is not possible to obtain a membrane-electrode composite with a good joined state between the electrode and the electrolyte membrane! Since it can be pressed in a dry state, the substantial contact area between the electrolyte membrane and the catalyst layer can be increased, and furthermore, there is almost no shrinkage of the electrolyte membrane due to moisture volatilization during heating press, so that the membrane of extremely excellent quality An electrode composite can be obtained, resulting in a high-performance fuel cell.
- Specific pressing methods include roll presses that specify pressure and clearance, and flat plate presses that specify pressure.
- the heating temperature can be selected appropriately according to the fluidity of the interfacial resistance-reducing composition. From the viewpoint of suppressing thermal decomposition of the polymer material having an ionic group or an ionic group, it is preferable to carry out the reaction in the range of room temperature to 130 ° C. In the case of a flat plate press in which pressurization is preferably as weak as possible from the viewpoint of electrolyte membrane and electrode protection, a range of 0.1 MPa to 10 MPa is preferable.
- an electrode catalyst layer may be formed on the interface resistance-reducing composition to form a membrane electrode assembly.
- the electrodes provided with the interfacial resistance reducing composition are pasted together as an interfacial resistance reducing composition / electrolyte film without preparing an electrolyte membrane again. It can also be set as a membrane electrode composite. In this case, it is preferable to apply the interface resistance reducing composition larger than the area of at least one of the electrodes, which is preferably thickened so that the coating weight of the interface resistance reducing composition is not short-circuited.
- the output of a fuel cell using an electrode composite tends to be improved, and the interface resistance reducing composition is also capable of reducing the interfacial resistance and the electrode or electrolyte membrane with less shrinkage when the plasticizer of the coating film is removed.
- the coating film made of the composition is excellent in that the interfacial adhesion is good.
- cleaning (extraction) removal with water or alcohol is preferred. Therefore, it is industrially preferable that the plasticizer is also water-soluble.
- the membrane electrode composite composited via the interfacial resistance-reducing composition has an adverse effect on the good solvent for the plasticizer and the member to be used such as the electrolyte membrane and the catalyst.
- the membrane electrode assembly is immersed in a solvent such as water, alcohol, or an aqueous alcohol solution for a certain period of time, extracted and removed with water vapor, and the membrane electrode assembly is removed from the fuel cell.
- the method for producing a membrane electrode assembly of the present invention can be applied to all electrolyte membranes such as perfluoro-based electrolyte membranes and hydrocarbon-based electrolyte membranes typified by Nafion (registered trademark) (manufactured by DuPont).
- electrolyte membranes such as perfluoro-based electrolyte membranes and hydrocarbon-based electrolyte membranes typified by Nafion (registered trademark) (manufactured by DuPont).
- Nafion registered trademark
- DuPont DuPont
- membranes having a glass transition temperature of 130 ° C or higher, a tensile modulus of lOOMPa or higher, and a moisture content of 40% by weight or lower including ionic group-containing polyphenoloxide, ionic group-containing polyether ketone, and ionic group.
- polymer materials can be used alone or in combination of two or more, and can be used as a polymer blend, a polymer alloy, or a laminated film of two or more layers.
- introduction method, synthesis method, and molecular weight range of the ionic group and ionic group here are as described above.
- a polymer material having a sulfonic acid group is most preferred as described above.
- — SO M group M is a metal
- the metal M may be any salt that can form a salt with sulfonic acid, but Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Ti, V can be used in terms of cost and environmental impact. Of these, Li, Na, K, Ca, Sr, and Ba are more preferred. Li, Na, and others are preferred among others, Mn, Fe, Co, Ni ⁇ Cu, Zn, Zr, Mo, and W. I like it. By forming a film in the state of these metal salts, heat treatment at a high temperature is possible, and this method is suitable for a polymer material system that can obtain a high glass transition point and a low water absorption rate.
- the temperature of the heat treatment is preferably from 100 to 500 ° C, more preferably from 200 to 450 ° C, and more preferably from 250 to 400 ° C, from the viewpoint of water absorption of the resulting film.
- a temperature of 100 ° C. or higher is preferable for obtaining a low water absorption rate.
- the temperature is 500 ° C. or lower, the polymer material can be prevented from being decomposed.
- the heat treatment time is preferably 10 seconds to 24 hours in terms of productivity, more preferably 30 seconds to 1 hour, and more preferably 45 seconds to 30 minutes. By setting the heat treatment time to 10 seconds or longer, it is possible to remove the solvent sufficiently and to obtain a sufficient fuel crossover suppression effect. In addition, when the time is shorter than 24 hours, the polymer is not decomposed and proton conductivity can be maintained, and the productivity is increased.
- Examples of the method for producing the electrolyte membrane include a method of applying a polymer solution by an appropriate coating method, removing the solvent, treating at a high temperature, and then treating with an acid.
- methods such as spray coating, brush coating, dip coating, die coating, curtain coating, flow coating, spin coating, and screen printing can be applied.
- a film can be formed by a wet coagulation method using a soot solvent, and in the absence of a solvent, a method of curing with light, heat, moisture, or the like, a method of heating and melting a polymer, cooling the film into a film, and the like can be applied.
- Examples of the solvent used for film formation include N, N dimethylacetamide, N, N dimethyl formamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, 1,3-dimethyl-2-imidazolidinone, Aprotic polar solvents such as hexamethylphosphonetriamide, ⁇ ⁇ ⁇ ⁇ ester solvents such as butyrolatatone and butyl acetate, carbonate solvents such as ethylene carbonate and propylene carbonate, ethylene glycol monomethyl etherenole, ethyleneglycolenomonoethylenoatenoate, An alcohol solvent such as propylene glycol monomethyleno ether, an alcoholylene glycol monoalkyl ether such as propylene glycol monomethenoate ethere, or isopropanol is preferably used.
- the film thickness of the electrolyte membrane to be used usually 3 to 2000 / ⁇ is preferably used. A thickness of more than 3 m is preferred to obtain a membrane strength that can withstand practical use. A thickness of less than 2000 m is preferred to reduce membrane resistance, that is, to improve power generation performance. A more preferable range of the film thickness is 5 to: LOOO ⁇ m, and a more preferable range is 10 to 500 ⁇ m.
- the film thickness can be controlled by various methods. For example, when forming a film by the solvent casting method, it can be controlled by the concentration of the solution or the coating thickness on the substrate, and when forming the film by the cast polymerization method, for example, the thickness of the spacer between the plates. Can also be prepared.
- the mechanical strength is improved, the thermal stability of the ionic group is improved, and the workability is improved within a range that does not impair the ionic conductivity and the effect of suppressing fuel crossover.
- it may contain fillers or inorganic fine particles, or may form networks or fine particles made of polymers or metal oxides, or it may be a film soaked in a support or the like. There is no problem.
- an electrode suitable for the membrane electrode assembly of the present invention comprises a catalyst layer and an electrode substrate.
- the catalyst layer here is a layer containing a catalyst for promoting an electrode reaction, an electron conductor, an ion conductor, and the like.
- a noble metal catalyst such as platinum, palladium, ruthenium, rhodium, iridium and gold is preferably used.
- One of these may be used alone, or two or more of them may be used in combination, such as an alloy or a mixture.
- Furnace Black includes Cabot Vulcan XC-72R (registered trademark), Nolecan P (registered trademark), Black Pearls 880 (registered trademark), Black Pearls 1100 (registered trademark), Black Pearls 1300 (registered trademark), Black Pa Alesylene 2000 (Registered Trademark), Regal 400 (Registered Trademark), Ketjen Black 'International Ketjen Black EC (Registered Trademark), EC600JD, Mitsubishi Igakusha # 3150, # 3250, etc.
- black include Denka Black (registered trademark) manufactured by Denki Kagaku Kogyo.
- the substance having ion conductivity (ion conductor) used in the catalyst layer various organic and inorganic materials are generally known. However, when used in a fuel cell, the ion conductivity is low. Polymers (ionic conductive polymers) having ionic groups such as sulfonic acid groups, carboxylic acid groups, and phosphoric acid groups that are improved are preferably used. Among these, from the viewpoint of the stability of the ionic group, a polymer having ion conductivity composed of a side chain of fluoroalkyl ether and a main chain of fluoroalkyl, or the polymer electrolyte material of the present invention is preferably used.
- the above-mentioned hydrocarbon polymer material may be effective in durability and the like from the viewpoint of methanol resistance.
- the ionic conductor Since the catalyst and the electronic conductors are usually powders, the ionic conductor usually plays a role of solidifying them.
- the ionic conductor may be added in advance to a coating liquid containing catalyst particles and an electronic conductor as main constituents when the catalyst layer is prepared, and applied in a uniformly dispersed state. Preferred is U ⁇ .
- the amount of the ionic conductor contained in the catalyst layer should be appropriately determined according to the required electrode characteristics and the conductivity of the ionic conductor used, and is not particularly limited. A range of 1 to 80% is preferable, and a range of 5 to 50% is more preferable. If the ionic conductor is too low, the ionic conductivity is too low, and if it is too high, the gas permeability may be hindered.
- the catalyst layer may contain various substances in addition to the catalyst, the electron conductor, and the ion conductor.
- a polymer other than the above-mentioned ion conductive polymer may be included in order to enhance the binding property of the substance contained in the catalyst layer.
- Such polymers include, for example, polyfluoride (PVF), poly (vinylidene fluoride) (PVDF), polyhexafluoropropylene (FEP), polytetrafluoroethylene, polyperfluoroalkyl vinyl ether.
- Polymers containing fluorine atoms such as (PFA), copolymers thereof, copolymers of monomer units constituting these polymers with other monomers such as ethylene and styrene, or blend polymers may be used. It can.
- the content of these polymers in the catalyst layer is preferably in the range of 5 to 40% by weight. If the polymer content is too high, the electron and ionic resistance increases and the electrode performance tends to decrease.
- the catalyst layer facilitates the discharge of by-products due to an electrode reaction that preferably has a structure that allows the liquid or gas to permeate. Structure is preferred.
- the electrode base material one that can collect current or supply power with low electrical resistance can be used. Further, when the catalyst layer is used also as a current collector, it is not necessary to use an electrode substrate.
- the electrode base material include carbonaceous and conductive inorganic substances. Examples thereof include, for example, fired bodies from polyacrylonitrile, fired bodies of pitch force, carbon materials such as graphite and expanded graphite, stainless steel, molybdenum, titanium, and the like. These forms are not particularly limited, and are used in the form of a fiber or particles, for example, but a fibrous conductive material (conductive fiber) such as carbon fiber is preferable from the viewpoint of fuel permeability. O Conductive fiber was used.
- a non-woven fabric carbonized or graphitized, a flameproofed yarn, or a mat non-woven fabric made by a paper making method using carbonized yarn or graphitic yarn is preferably used.
- Examples of the carbon fibers used for the electrode substrate that can be used include polyacrylonitrile (PAN) -based carbon fibers, phenol-based carbon fibers, pitch-based carbon fibers, and rayon-based carbon fibers.
- PAN polyacrylonitrile
- the powerful electrode base material has a water repellency treatment for preventing gas diffusion due to stagnation of water and a decrease in permeability, a partial water repellency for forming a water discharge path, a hydrophilic treatment,
- carbon powder can be added to lower the resistance.
- a conductive intermediate layer containing at least an inorganic conductive material and a hydrophobic polymer can be provided between the electrode substrate and the catalyst layer.
- the electrode base material is a carbon fiber woven fabric or a nonwoven fabric having a large porosity, by providing a conductive intermediate layer, it is possible to suppress performance degradation due to the catalyst layer soaking into the electrode base material.
- Rr can be used as an index of the interfacial resistance of the membrane electrode assembly of the present invention. Rr will be described in detail in Section 6 etc. of [Measurement Method] below.
- Fuels for fuel cells using the membrane electrode assembly produced by the method of the present invention include oxygen, hydrogen and methane, ethane, propane, butanemethanol, isopropyl alcohol, acetone, glycerin, ethylene glycol, formic acid. And organic compounds having 1 to 6 carbon atoms such as acetic acid, dimethyl ether, hydroquinone, and cyclohexane, and a mixture of these with water, and one or a mixture of two or more may be used.
- the power of power generation and the simplification of the entire battery system Hydrogen and a fuel containing an organic compound having 1 to 6 carbon atoms are preferably used, and hydrogen and aqueous methanol are particularly preferable in terms of power generation efficiency.
- the methanol concentration is appropriately selected depending on the fuel cell system to be used, but a higher concentration as much as possible is preferable from the viewpoint of long-time driving.
- an active fuel cell with a system that sends a medium necessary for power generation such as a liquid feed pump or blower fan, to a membrane electrode assembly, or an auxiliary machine such as a cooling fan, a fuel dilution system, or a product recovery system
- Concentration 30 ⁇ Passive type fuel cell without auxiliary equipment that is preferable to inject fuel of more than LOO% by fuel tank or fuel cassette, dilute to about 0.5 ⁇ 20% and send it to membrane electrode assembly Is preferably a fuel having a methanol concentration of 10 to 100%.
- the membrane electrode assembly of the present invention is a membrane electrode assembly in which an electrolyte membrane is interposed between a pair of electrodes, and has a layer (A) between at least one electrode and the electrolyte membrane, and has an ultrafine hardness.
- the storage elastic modulus of the electrolyte membrane measured by the meter is C and the storage elastic modulus of the layer (A) is D, the value of the storage elastic modulus C is lGPa or more.
- a material substantially the same as the high molecular material having an ionic group in the above-mentioned interface resistance reducing composition can be used.
- the material that is substantially the same as the polymer material having an ionic group in the interface resistance reducing composition means that the main component is the same material.
- the material having the same main component here means that 50% by weight or more of the constituent material is the same material.
- types of groups that bind aromatic rings such as polyetheretherketone and polyetherketone If they are the same, they can be made of the same material.
- the materials constituting the electrolyte membrane and the layer (A) are substantially the same.
- the electrolyte membrane and the layer (A) are mixed with different additives and polymer materials, or have different substituents or derivatives thereof, other components are copolymerized.
- 50% by weight or more of the material constituting the electrolyte membrane and the layer (A) is the same material, it can be judged that the material is substantially the same.
- the density and type of the ionic group of the polymer material having the ionic group constituting the electrolyte membrane and the layer (A) are different! /
- the same material can be used as long as the types of groups connecting the aromatic rings such as polyetheretherketone and polyetherketone are the same.
- the storage elastic modulus in the present invention indicates that the rigidity indicating the rigidity of the material is high. That is, the higher the storage elastic modulus, the higher the resistance to fuel and the higher the heat resistance. Ascertained and reached the present invention. In other words, in order to suppress fuel crossover, it is important to suppress swelling with respect to fuel, but there is a correlation between this swelling suppression effect and storage elastic modulus, and in particular, storage of the electrolyte membrane constituting the membrane electrode assembly. If the elastic modulus C is greater than lGPa, the fuel crossover suppression effect is high.
- the storage elastic modulus C of the electrolyte membrane is preferably 2 GPa or more, more preferably 3 GPa or more.
- the storage elastic modulus D of the layer (A) is also 1 GPa or more, the effect of suppressing the fuel crossover can be further enhanced, so it is preferable.
- the storage elastic modulus D is more preferably 2 GPa or more.
- the viscoelastic physical strength of the material such as the electrolyte membrane and the layer (A) measured by using an ultra-micro hardness meter is extremely correlated with the superiority or inferiority of the fuel crossover. Since the absorption of the material was considered to be the force that initiates the surface force of the material, the present inventors focused on the viscoelastic properties of the extreme surface and completed the present invention.
- the storage elastic modulus was measured using a microhardness meter (Tribo Indenter manufactured by Hysitron) with a modular mapping image [storage elastic modulus (E,) image 'loss elastic modulus (E ,,)
- the membrane electrode composite is embedded and cured with an electron microscope epoxy resin (Q U etol 812 manufactured by Nissin EM Co.), and then the membrane electrode composite is formed using an ultramicrotome (Leica Ultracut S). An ultrathin section with a cross-section is prepared and used as a measurement sample, measured under the following conditions, and elastic modulus is calculated using Hertz's contact theory.
- Tribo Indenter manufactured by Hysitron
- Measurement field of view approx. 30 mm square
- ⁇ is the projected area of the impression formed by contact between the sample and the indenter
- E * is the combined elastic modulus of the indenter system and the sample system.
- the tip of the indenter when the indenter contacts the very surface of the sample, the tip of the indenter is regarded as a spherical shape, and it is considered that Hertz's contact theory relating to the contact between the spherical shape and the semi-infinite flat plate can be applied.
- Hertz's contact theory the radius a of the indentation projection surface when the indenter is in contact with the sample is expressed by Equation (2).
- Modulus mapping is based on the Hertzian contact theory described above, in which an indenter is brought into contact with the very surface of the sample, the indenter is microvibrated during the test, and the response amplitude and phase difference with respect to vibration as a function of time. This is a method to obtain K (measurement system stiffness) and D (sample damping).
- Equation (4) the first term is the force derived from the indenter shaft (m: mass of the indenter shaft), Equation (4), the second term is the force derived from the viscous component of the sample, and Equation (4)
- the third term represents the stiffness of the sample system, and t represents time. Since F (t) in Equation (4) depends on time, it is expressed as in Equation (5).
- E * is regarded as the storage elastic modulus (E '), and the formulas (1) to (10) are summarized.
- Formula (11) force also calculated storage elastic modulus.
- the loss elastic modulus of the electrolyte membrane is ⁇ and the loss elastic modulus of the layer ( ⁇ ) is F, either of the loss elastic modulus ⁇ and F is 0. lGPa or higher is preferred.
- the loss elastic modulus indicates the viscosity of the material, and its value is large and tends to be strong and difficult to break!
- the loss elastic modulus in the present invention can also be measured in the same manner as the storage elastic modulus measurement described above.
- Ks derived from the sample is used, and the equation (11) The combined equation (12) was calculated.
- At least either CZD or EZF is 0.5.
- CZD and EZF are viscoelastic property ratios between the electrolyte membrane and the layer (A), and indicate the degree of deformation of each layer at the bonded interface. If the membrane electrode assembly of the present invention is used as a fuel cell, the degree of deformation of the electrolyte membrane and the layer (A) is the same in various fuel cell operating environments. It can be reduced and durability can be improved. More preferred is 0.7 to 1.4, and even more preferred is 0.8 to 1.3. Furthermore, if both CZD and EZF are 0.5 to 1.5, peeling and deformation can be further reduced, and durability is further improved. Therefore, both CZD and EZF are preferably 0. 7 to 1.4, and more preferably, both CZD and EZF are 0.8 to 1.3.
- the membrane electrode assembly of the present invention comprises an electrolyte membrane between a pair of electrodes, and the phase difference measured by tapping mode scanning of a scanning probe microscope is between the electrolyte membrane and at least one electrode and the electrolyte membrane.
- the substantially different layer (A) has an electrolyte membrane and the layer (A) contain an aromatic hydrocarbon having a diionic group.
- the phase difference in the present invention is an index of softness and can be measured by the following method. For example, after embedding a membrane electrode composite with epoxy resin for electron microscopy (Q U etol 812 manufactured by Nissin EM) and curing it, the cross section of the membrane electrode composite with an ultramicrotome (Ultracut S manufactured by Leica) is used. Can be measured by tapping mode scanning of a scanning probe microscope.
- the tapping mode in the present invention is "scanning probe microscope for nanotechnology"
- the phase difference distribution in the scanning range can be output.
- the phase difference is large and the interaction force is small. Is detected with a small phase difference. That is, a relatively soft portion in the sample has a large phase difference and a hard portion has a small phase difference. Therefore, the phase difference is an index representing the softness of the surface.
- the membrane electrode assembly of the present invention has a layer (A) having a phase difference substantially different from that of the electrolyte membrane, and the electrolyte membrane and the layer (A) have a ionic group in the main chain.
- Aromatic hydrocarbons having Here, the phase difference is substantially different from the first decimal point of the absolute value of the phase difference of each layer (electrolyte membrane layer and layer (A)) when measuring the electrolyte membrane and the layer (A) in the same field of view. Means different places.
- phase difference is substantially different from that of the electrolyte membrane (A), and the electrolyte membrane and the layer
- (A) should be a membrane electrode composite containing an aromatic hydrocarbon having an anionic group in the main chain. Even if the characteristics of the individual members of the electrode and the electrolyte membrane to be used are excellent, the inventors have the performance of the membrane electrode assembly as a result if the resistance between the electrode and the electrolyte membrane is large when combined. As a result, the inventors have found that this is insufficient, and have reached the present invention.
- the electrolyte membrane in order to suppress fuel crossover of the electrolyte membrane, improve durability at high temperatures, and improve mechanical strength, it has a high heat resistance with a glass transition point of 120 ° C or higher due to dynamic viscoelasticity, a tensile elastic modulus of lOOMPa or higher,
- the electrolyte membrane tends to be rigid because a molecular structure that provides a high modulus of elasticity of 500 MPa or more, more preferably lOOOMPa or more, and a low water content of 100% or less with respect to the weight of the electrolyte membrane is preferable. There is. For this reason, it is necessary to use an electrolyte membrane having an aromatic hydrocarbon having the above-mentioned performance and having a viewpoint of productivity and workability as a main component and having an aromatic group.
- fuel crossover can be suppressed and the mechanical strength can be maintained between the electrolyte membrane and the electrode, and at least a part of the fine void between the electrode and the electrolyte membrane can be filled, and the catalyst surface shape can be improved.
- a layer that can improve the followability by the electrolyte and substantially increase the contact area between the electrode and the electrolyte membrane, i.e., the phase difference of the electrolyte membrane is substantially different, and the aromatic carbonization having an anionic group in the main chain A layer of polymer material containing hydrogen was provided.
- the electrode and the electrolyte membrane are attached with an ordinary adhesive or a perfluorinated proton conductive polymer.
- the electrolyte membrane and the layer (A) having a substantially different phase difference from the electrolyte membrane have an anionic group in the main chain.
- the aromatic hydrocarbon having an anionic group in the main chain means a unit in which an anionic group is directly bonded to an aromatic ring. The reason why the eron group is present in the main chain of the aromatic hydrocarbon is that the effect of suppressing the fuel crossover is great.
- the above-described aromatic group is present in the main chain of the aromatic hydrocarbon because the aromatic carbon of the main chain is rigid and difficult to move. Because the anionic group is directly bonded to hydrogen, for example, even if an aqueous methanol solution enters the polymer, the portion having the anionic group cannot move freely, resulting in a polymer. The rate at which the fuel can enter can be suppressed and fuel crossover can be reduced.
- the phase difference (M) of the electrolyte membrane and the phase difference (I) of the layer (A) in which the phase difference is substantially different from the electrolyte membrane are larger.
- the flexibility of the layer (A) whose phase difference is substantially different from that of the electrolyte membrane is changed in order to increase the contact area with the electrode in the production process of the membrane electrode assembly. Also good.
- the main component of the material constituting the layer (A) whose phase difference is substantially different from that of the electrolyte membrane of the membrane electrode assembly of the present invention is substantially the same. It is preferable that the adhesive strength at the interface of the layer (A) having a phase difference substantially different from that of the electrolyte membrane is substantially the same as the material strength.
- substantially the same material means that 50% by weight or more of the constituent material is the same material.
- the electrolyte membrane and the layer (A) may be mixed with different additives or polymer materials, may have different substituents or derivatives thereof, may be copolymerized with other components, If 50% by weight or more of the materials constituting the electrolyte membrane and the layer (A) are the same material, it can be judged that they are substantially the same material. As described above, even if the density and type of the ionic group of the polymer material containing an aromatic hydrocarbon having an anionic group in the main chain constituting the electrolyte membrane and the layer (A) are different, If the main chain skeletons of the polymer material are the same, they can be handled as the same material. For example, if the types of groups that bind aromatic rings such as polyether ether ketone and polyether ketone are the same, the same material is used. There is no problem.
- polymer material containing an aromatic hydrocarbon having an anionic group in the present invention will be described.
- the eron group one having proton exchange ability is preferable.
- Such functional groups include sulfonic acid groups (—SO (OH)), sulfate groups (—OSO (OH)), sulfone
- Two or more kinds of these ionic groups can be contained in the polymer material, and it may be preferable to combine them.
- the combination is appropriately determined depending on the structure of the polymer.
- the point of high proton conductivity has at least one of a sulfonic acid group, a sulfonimide group, and a sulfuric acid group.
- the point of hydrolysis resistance also has at least a sulfonic acid group.
- the density of the sulfonic acid group is preferably 0.1 to 5.
- OmmolZg more preferably 0.5 to 3.5 mmolZg, more preferably from the viewpoint of proton conductivity and fuel crossover suppression. Preferably, it is 1.0 to 3.5 mmol Zg.
- sulfonic acid group density 0. ImmolZg or higher, a high output density can be taken out, and 5.
- OmmolZg or lower to allow direct contact with liquid fuel such as a direct methanol fuel cell. fuel When used in a battery, it is possible to prevent the interface resistance reducing layer from being excessively swollen by the fuel and eluting or flowing out.
- the sulfonic acid group density is as described above.
- aromatic hydrocarbons having an anionic group in the main chain include mechanical strength, fuel durability, heat resistance, etc. of the layer (A) whose phase difference is substantially different from that of the electrolyte membrane.
- aromatic hydrocarbon polymers such as imide, polyimidazole, polyoxazole, and polyphenylene, in which an anionic group is introduced into an aromatic ring of the main chain.
- Ether ether ketone polyether ether ketone containing a component derived from 4,4, -dihydroxytetraphenol, polyether ether ketone containing a component derived from 4,4'-dihydroxybenzophenone, and 4,4 ' It is particularly preferred that the polyetherketone power containing a component derived from dihydroxybenzophenone is selected. These can be used alone or in combination of two or more, and can be used as a polymer blend or a polymer alloy.
- the membrane electrode assembly of the present invention used for these fuel cells has a layer (A) 12 that follows the irregularities of the catalyst layer 4. It is pasted in a state where it is interposed.
- Fig. 7 shows an example of a passive fuel cell that does not use an auxiliary machine.
- the fuel cell may be built in the device to be used, or may be used as an external unit. From the viewpoint of maintenance, it is also preferable that the membrane electrode assembly is detachable from the fuel cell.
- the fuel cell performance of the present invention differs depending on the device to be driven because the fuel and air supply method, cell shape, flow channel shape, current collection method, electronic circuit design, etc. differ.
- the size, number, series and number of Z or parallel, etc. are preferably selected according to the equipment design as appropriate.
- the resistance of the produced membrane electrode assembly can be set in a fuel cell and measured using a frequency response analyzer 1255B manufactured by Solartron and a potentiostat SI1287.
- a frequency response analyzer 1255B manufactured by Solartron and a potentiostat SI1287.
- current I (mA) and amplitude iZlO (mA) are applied to the membrane electrode assembly, measurement is performed in the frequency range of 50 kHz to lOmHz, and impedance is measured.
- the right end and the left end of the obtained X-axis intercept are the right end and the left end of the intersection with the X axis of the semicircle obtained from the complex plane graph force, respectively. If it is not a semicircle, use a Nyquist plot to estimate the semicircle from the circular fit of ZVie w Electrochemical Impedance Software (bcnbner Associates, Inc.) and use the right and left edges of its X-axis intercept (see Figure 1). ).
- the resistance Rr greatly depends on the applied current value and amplitude.
- the membrane electrode composite membrane of the present invention preferably uses a 3% by weight aqueous methanol solution and has an Rr of 1.5 ⁇ 'cm 2 or less when the cell temperature is 60 ° C. 2 ⁇ ′cm 2 or less is more preferable 1.0 ⁇ ′cm 2 or less is more preferable.
- the power density is preferably 40mWZcm 2 or more. If it is 40 mWZcm 2 or more, the area of the membrane electrode assembly can be reduced, and the range of devices that can be driven is wide and useful. 50 mWZcm 2 or more is more preferable. 60 mWZcm 2 or more is more preferable.
- the device can be used for a long time when it is mounted on a device as a fuel cell.
- the voltage drop rate is preferably 50% or more, more preferably 60% or more, and further preferably 70% or more.
- the above output density can also be measured using, for example, an evaluation device manufactured by Toyo Corporation, a potentiostat manufactured by solartron 1470, and a frequency response analyzer manufactured by solartron 1255B.
- the exhaust gas from the force sword is collected in a gas collection bag and oxidized with methanol in the sampling gas using a gas chromatograph with an autosampler manufactured by Jell Science. both concentrations of the resulting diacid I ⁇ oxygen using methanol permeation amount force 3 wt% of aqueous methanol solution measured calculated membrane electrode assembly, when the cell temperature 60 ° C, at 10 molZcm 2 Zmin less Preferably there is. If it is less than 10 / z molZc m 2 / min, it is also useful from the viewpoint of extending the drive time of the on-board equipment that is less affected by the output drop at the fuel crossover. 8 ⁇ molZcm 2 Zmin or less is more preferable, and 5 molZcm 2 Zmin or less is more preferable.
- the power density with 30% by weight methanol aqueous fuel is the area of the membrane electrode assembly. Is more preferable than 40 mWZcm 2, more preferably 15 mWZcm 2 or more, and more preferably 20 mWZcm 2 .
- a power supply source of a moving body is preferable.
- the weight average molecular weight of the polymer was measured by GPC.
- Tosoh's HLC-8022GPC is used as an integrated UV detector and differential refractometer, and Tosoh's TSK gel Super HM-H (inner diameter 6. Omm, length 15cm) is used as the GPC column.
- Pyrrolidone solvent N-methyl-2-pyrrolidone solvent containing 10 mmol / L of lithium bromide
- the sample was prepared by immersing the polymer formed into a film in water at 25 ° C for 24 hours and cutting it into a strip of about 5 cm in length and 2 mm in width.
- the water used for washing was analyzed with a gas chromatograph “5890 series IV” manufactured by Hewlett Packard.
- the measurement conditions are as follows.
- the right end and the left end of the X-axis intercept obtained are the right end and the left end of the intersection point with the X axis of the semicircle obtained from the complex plane graph, respectively. If it is not a semicircle, use a Nyquist plot; et al. From ZView Electrochemical Impedance software (Scribner Asso dates, Inc.) to estimate the semicircle and use the right and left edges of its X-axis intercept.
- Fig. 1 shows an example of the impedance measurement result of the membrane electrode assembly.
- the resistance Rr greatly depends on the current value and amplitude to be applied, in the measurement method of the present invention, a 3 wt% methanol (MeOH) aqueous solution is supplied at 0.5 mlZmin to the anode side, and the air is supplied to the force sword side.
- MeOH methanol
- the cell temperature was set to 60 ° C, and the product of the current density value at the maximum output when measuring the voltage-current characteristics and the evaluated electrode area I (mA) was applied.
- Rr greatly depends on the interfacial resistance
- Rr is an index representing the effect of using the composition for reducing interfacial resistance of the present invention, and should be small.
- the membrane electrode assembly dried under reduced pressure at 60 ° C for 24 hours is cut out with a cutter, embedded in electron microscope epoxy resin (Quetol 812 manufactured by Nissin EM Co.), and in 48 ° C in an oven at 60 ° C for 48 hours. After curing the epoxy resin, an ultrathin section having a thickness of about 100 ⁇ m was prepared with an ultramicrotome (Ultracut S manufactured by Leica).
- the prepared ultrathin section was mounted on a 100 mesh Cu grid manufactured by Oken Shoji Co., Ltd., and TEM observation was performed at 100kV acceleration voltage using Hitachi transmission electron microscope H-7100FA. The cross section was observed to confirm the location of the electrolyte membrane and layer (A).
- a modulus mapping image of the electrolyte membrane part and layer (A) part was obtained using an ultra-micro hardness tester (Tribo Indenter manufactured by Hysitron), and storage modulus and loss modulus were calculated. Calculated.
- the storage elastic modulus of the electrolyte membrane is C
- the storage elastic modulus of the layer (A) is D and its ratio C / D
- the loss elastic modulus E of the electrolyte membrane is the value of the storage elastic modulus F of the layer (A) and its ratio.
- the ratio EZF was determined. The measurement conditions are shown below.
- Tribo Indenter manufactured by Hysitron
- Measurement field of view approx. 30 mm square
- the membrane electrode assembly dried under reduced pressure at 60 ° C for 24 hours is cut out with a cutter, embedded in electron microscope epoxy resin (Quetol 812 manufactured by Nissin EM Co.), and in 48 ° C in an oven at 60 ° C for 48 hours. After curing the epoxy resin, an ultrathin section having a thickness of about 100 ⁇ m was prepared with an ultramicrotome (Ultracut S manufactured by Leica).
- the prepared ultrathin section was mounted on a 100 mesh Cu grid manufactured by Oken Shoji Co., Ltd., and TEM observation was performed at 100kV acceleration voltage using a Hitachi transmission electron microscope H-7100FA. By observing the cross section, the location of the layer (A) having a different phase difference from the electrolyte membrane was confirmed.
- the cross-section cut with a microtome was ultrasonically cleaned with ethanol, and the measurement location of the electrolyte membrane and layer (A) was determined with reference to the TEM observation image, respectively. Measurement was performed using a Dimension 3000) and phase detection extender module (PHASE-D01 type). The scanning range was 12.5 m X 25 m, and the sample surface was moved while vibrating the measurement probe at the resonance frequency (tapping mode scanning). At this time, the radius of curvature of the probe tip was 5 to 20 nm, and the tabing frequency was 150 to 450 kHz.
- phase difference ratio is the brightest part of the observation sample excluding the constituents of the membrane electrode complex, that is, the membrane electrode.
- M is the hardened epoxy resin used when preparing ultra-thin slice samples of the polar composite, and M Expressed in ZI.
- Membrane electrode assembly is installed in Electrochem single cell "EFC05-01SP" (cell for 5cm 2 electrode area), cell temperature is 50 ° C, 20% methanol aqueous solution at the anode side at a rate of 0.5ml / min. Supply the synthetic air to the force sword side at a speed of 50mlZ, and measure the voltage and current characteristics using the evaluation device made by Toyo Techni Power, the potentiostat 1470 made by solartron, and the frequency response analyzer made by solartron 1255B.
- the synthetic air discharged from the force sword is collected in a gas collection bag, and methanol in the sampling gas is collected using a gas chromatograph 'MicroGC CP4900' with an autosampler manufactured by GL Sciences.
- concentration of both carbon dioxide produced by oxidation was calculated by assuming that all the carbon dioxide originated from the permeated methanol.
- Min the total concentration of methanol and diacid carbon by gas chromatograph is Z (volume%) and the total volume is V (ml), and the open area (the area where the methanol aqueous solution fuel in the membrane electrode assembly is in direct contact)
- Viscosity was measured between temperatures 20 ° C ⁇ 100 ° C under the condition of using a rotary viscometer (Rheotech Co. rheometer RC20 type) shear rate 35 (s _ 1).
- the temperature dependence of the viscosity change was determined by the ratio YZX of the value X (Pa) at 30 ° C and the value Y (Pa) at 80 ° C.
- the lOh reaction was performed at 0 ° C. Then, it was poured into a large amount of water little by little and neutralized with NaOH, and then 200 g of sodium chloride was added to precipitate the composite. The resulting precipitate was separated by filtration and recrystallized with an aqueous ethanol solution to obtain disodium 3, 3, 1-disulfonate-4, 4, 4-dibenzo benzophenone. (Yield 181 g, yield 86%).
- the above polymer A was dissolved in N, N-dimethylacetamide to obtain a coating solution having a solid content of 25%.
- the coating solution was cast on a glass plate and dried at 70 ° C for 30 minutes and further at 100 ° C for 1 hour to obtain a 72 m film.
- the temperature was raised to 200 to 300 ° C for 1 hour, heat-treated at 300 ° C for 10 minutes, allowed to cool, and immersed in 1N hydrochloric acid for 12 hours or more to protonate
- the membrane was immersed in a large excess amount of pure water for 1 day or more and thoroughly washed to obtain an electrolyte membrane A.
- the tensile modulus of the film was 1300 MPa.
- Polymer B was similarly formed to obtain electrolyte membrane B.
- the tensile elastic modulus of the electrolyte membrane was 131 OMPa.
- PT FE treatment was performed on carbon cloth manufactured by E-TEK Co., Ltd., which has carbon fiber weaving ability. Specifically, carbon cloth was dipped in an aqueous dispersion containing 20% by weight of polytetrafluoroethylene (hereinafter abbreviated as PTFE), pulled up, dried, and fired. One side was coated with a carbon black dispersion containing 20% by weight of PTFE and baked to prepare an electrode substrate. On this electrode substrate, Pt—Ru supported carbon catalyst “HiSPEC” (registered trademark) 7000 and “HiSPEC” (registered trademark) 6000 manufactured by Johnson Massey (Johson & Matthey), and 20% “naphth ion manufactured by DuPont”.
- HiSPEC registered trademark
- HiSPEC registered trademark
- An anode catalyst coating solution consisting of “(“ Nafion ”) (registered trademark) solution and n-propanol was applied and dried to prepare an electrode A.
- the anode catalyst coating solution was applied to the surface coated with the carbon black dispersion.
- a force sword catalyst coating solution consisting of a Pt-supported carbon catalyst TEC10V50E made by Tanaka Kikinzoku Kogyo Co., Ltd. (Naphion) (registered trademark) (Naphion (registered trademark)) solution is applied to the above electrode base material. It was coated and dried to produce Electrode B.
- a catalyst-supported carbon (catalyst: Pt, carbon: Cabot ValcanXC-72, platinum loading: 50% by weight) is added to Aldrich's “Nafion” (registered trademark) solution.
- the catalyst polymer composition was prepared by adding the mixture so that the weight ratio was 1: 0.5 and stirring well.
- the catalyst-polymer composition was previously treated with a water repellent treatment (impregnated with 20% by weight of PTFE). It was applied to an electrode base material (carbon paper TGP-H-060 manufactured by Toray Industries, Inc.) that had been fired, and immediately dried to prepare electrode C.
- composition A 10 g of polymer A as a polymer material having an ionic group, 60 g of N-methyl-2-pyrrolidone and 40 g of glycerin as plasticizers were placed in a container and stirred until uniform to obtain composition A with reduced interface resistance.
- YZX which represents the temperature dependence of the viscosity change of Composition A having reduced interface resistance, was 0.08.
- This interfacial resistance-reducing composition A was applied onto electrode A and electrode B to 3 mgZcm 2 and heat-treated at 100 ° C. for 1 minute. These electrodes were cut to have an electrode area of 5 cm 2 .
- these electrodes with the interfacial resistance reducing composition A are laminated so that the interfacial resistance reducing composition A is on the electrolyte membrane A side, and heated at 100 ° C for 1 minute at a pressure of 5 MPa.
- the membrane electrode assembly was obtained by pressing.
- the pressed membrane electrode assembly was immersed in 50 ml of pure water for 30 minutes, and the plasticizer remaining in the interfacial resistance-reducing composition A was extracted and washed, and incorporated into a power generation cell to obtain a fuel cell.
- the voltage holding ratio of the membrane electrode composite is that the initial voltage is 0.25 V after 100 hours constant current power generation. The voltage was 0.24V and showed an excellent durability of 96%.
- the methanol permeation amount of this membrane electrode assembly was 4.5 ⁇ mol Zcm 2 Z min.
- the output of a passive evaluation showed 40mWZcm 2.
- Electrode A, electrode B and electrolyte membrane A were laminated so as not to use an interface resistance reducing composition, and heated and pressed at 100 ° C for 8 minutes at a pressure of 5 MPa to obtain a membrane electrode composite.
- Figure 2 shows the voltage-current characteristics of a fuel cell using this. The Rr value was 2.5 Q -cm 2 .
- Example 1 showed better voltage-current characteristics than Comparative Example 1. Attempts were made to measure the storage elastic modulus, loss elastic modulus, and phase difference of the cross section of this membrane electrode composite, and it was found that only the electrolyte membrane portion could be observed.
- This membrane electrode composite had a methanol permeation of 4 ⁇ molZcm 2 Z min. The output of this membrane electrode composite in the passive evaluation was 5 mWZcm 2 .
- composition B 10 g of polymer A as a polymer material having an ionic group, 40 g of N-methyl-2-pyrrolidone and 40 g of glycerin as plasticizers were placed in a container and stirred until uniform to obtain composition B with reduced interface resistance.
- Figure 8 shows the temperature dependence of the viscosity of Composition B for reducing interfacial resistance.
- YZX which represents the temperature dependence of the viscosity change of Composition B for reducing interfacial resistance, was 0.05.
- This interfacial resistance-reducing composition B was applied to a release substrate at 3 mg / cm 2 and heat-treated at 100 ° C. for 1 minute to prepare a release sheet with an interfacial resistance-reducing composition.
- This release sheet with the interface resistance reducing composition is superimposed on electrode A and electrode B, and heated and pressed at 100 ° C for 1 minute at a pressure of 2 MPa, the release paper is peeled off, and the electrode with the interface resistance reducing composition is attached. Got. These electrodes were cut so as to have an electrode area of 5 cm 2, and a membrane electrode assembly was obtained in the same manner as in Example 1. A fuel cell using this was fabricated and evaluated in the same manner as in Example 1. The voltage-current characteristics almost overlapped with Example 1, and the maximum output was 102 mWZcm 2 . The Rr value was 0.8 ⁇ 'cm 2 .
- the voltage holding ratio of the membrane electrode composite was 0.26V at the initial voltage, and 0.25V after 100 hours of constant current power generation, showing excellent durability of 96%.
- the methanol permeation amount of this membrane electrode assembly was 4.0 ⁇ mol Zcm 2 Z min.
- the output of a passive evaluation showed 39mWZcm 2.
- a release sheet with the interfacial resistance-reducing composition B of Example 2 was prepared.
- This release sheet with the interfacial resistance reducing composition B is cut to a 2.4 cm square, and the interfacial resistance reducing composition B and the electrolyte membrane A are in contact with each other and pasted on both sides at 60 ° C.
- the release substrate was peeled off.
- electrodes A and B with an electrode area of 5 cm 2 were layered on the surface of the electrolyte resistance reducing composition layer provided on both sides of the electrolyte membrane, and heated and pressed at 100 ° C for 1 minute at a pressure of 2 MPa. As a result, an electrode with an interface resistance reducing composition was obtained.
- Example 2 When a fuel cell using this was fabricated and evaluated in the same manner as in Example 1, the voltage-current characteristics almost overlapped with Example 1, and the maximum output was 99 mWZcm 2 . The Rr value was 0.85 ⁇ 'cm 2 .
- the storage elastic modulus, loss elastic modulus and phase difference of the cross section of this membrane electrode composite were measured, a layer (A) having a phase difference different from that of the electrolyte membrane portion could be confirmed, and the phase difference ratio MZI was 1.11.
- the storage elastic modulus C of the electrolyte membrane portion is 7.5 GPa
- the loss elastic modulus E is 1.8 GPa
- the storage elastic modulus D of the layer (A) portion is 8.8 GPa
- the loss elastic modulus F is 1.7 GPa.
- the initial voltage was 0.26V
- the voltage after 100 hours constant current power generation was 0.25V, which showed an excellent durability of 96%.
- a release sheet with the interface resistance-reducing composition B was prepared.
- This interfacial resistance reducing composition B-attached release sheet is superimposed on electrode A and electrode B, heated at 100 ° C for 1 minute and heated at 2 MPa, peeled off the release paper, and interface resistance reducing composition B An attached electrode was obtained.
- These electrodes are cut to an electrode area of 5 cm 2 and 20% methanol After being immersed in an aqueous solution for 5 hours, the plasticizer and solvent in the interface resistance reducing composition B were extracted and removed by washing with pure water. Next, the electrolyte membrane A was sandwiched between these electrodes, and heated and pressed at 130 ° C for 1 minute at a pressure of 5 MPa to obtain a membrane electrode composite.
- Example 2 A fuel cell using this was fabricated and evaluated in the same manner as in Example 1.
- the voltage-current characteristics almost overlapped with Example 1, and the maximum output was 105 mWZcm 2 .
- the Rr value was 0.79 Q-C m 2 .
- the storage elastic modulus, loss elastic modulus and phase difference of the cross section of this membrane electrode assembly were measured, a layer (A) having a phase difference different from that of the electrolyte membrane portion was confirmed, and the phase difference ratio M o. 95 was obtained.
- the storage elastic modulus C of the electrolyte membrane portion is 9.2 GPa
- the loss elastic modulus E is 1.4 7 GPa
- the storage elastic modulus D of the layer (A) portion is 8.8 GPa
- the loss elastic modulus F is 1.8 GPa
- C / ⁇ 1.04
- E / F 0.82.
- the membrane electrode composite had an Rr value of 0.8 ⁇ ⁇ cm 2 .
- the storage elastic modulus, loss elastic modulus and phase difference of the cross section of this membrane electrode assembly were measured, a layer (A) having a phase difference different from that of the electrolyte membrane portion could be confirmed, and the phase difference ratio MZI was 0.99.
- the storage elastic modulus C of the electrolyte membrane part is 0.8 GPa
- the loss elastic modulus E is 0.06 GPa
- the storage elastic modulus D of the layer (A) part is 0.7 GPa
- the loss elastic modulus F is 0.05 GPa.
- DuPont's "Nafion 117 (registered trademark)" is used as the electrolyte membrane, and these electrodes with the interface resistance reducing composition A are the interface resistance reducing composition A on the electrolyte membrane side.
- the membrane electrode composite was obtained by heating and pressing at 100 ° C for 5 minutes at a pressure of 5 MPa. The pressed membrane electrode assembly was immersed in 50 ml of pure water for 30 minutes, and the plasticizer remaining in the interfacial resistance reducing composition A was extracted and washed, and incorporated into a power generation cell to obtain a fuel cell.
- the Rr value of this membrane electrode composite was 0.9 ⁇ ′cm 2 .
- the storage elastic modulus, loss elastic modulus, and phase difference of the cross section of the membrane electrode assembly were measured, a layer (A) having a phase difference different from that of the electrolyte membrane portion could be confirmed, and the phase difference ratio MZI was 12.8.
- the storage elastic modulus C of the electrolyte membrane part is 0.8 GPa
- the loss elastic modulus E is 0.06 GPa
- the storage elastic modulus D of the layer (A) part is 9.2 GPa
- the loss elastic modulus F is 1.7 GPa.
- this membrane electrode composite was smaller than the storage elastic modulus C force GPa of the electrolyte membrane, the methanol permeation amount with a large methanol aqueous fuel penetration was 14 molZcm 2 Z, and the methanol suppression effect was small.
- the initial voltage was 0.17V
- the voltage after 100 hours constant current power generation was 0.08V
- the durability was inferior at 47%.
- the output in the noisy evaluation was 8 mWZcm 2 , which was a low output.
- the evaluation cell after these evaluations was disassembled, and the membrane electrode assembly was taken out and visually observed. Separation occurred at the interface of the membrane, which was thought to be caused by different dimensional changes due to the swelling of the methanol aqueous solution of each constituent material.
- the current density that is, the electrode reaction rate is increased, the degree of non-equilibrium in the process that does not proceed easily becomes very large and eventually reaches the physical limit. That is, a force that makes it impossible to obtain a current density higher than this.
- This current density is the limiting current density.
- the membrane electrode composite produced via the interfacial resistance reducing composition has a larger maximum output in the range of the tensile modulus of elasticity.
- the tensile modulus of elasticity is lOOMPa. If it becomes above, the effect will become remarkable.
- a membrane electrode assembly was produced in the same manner as in Example 3 except that the electrolyte membrane A in Example 3 was changed to the electrolyte membrane B.
- the voltage holding ratio of the membrane electrode composite was 0.26V at the initial voltage, and 0.25V after 100 hours constant current power generation, showing an excellent durability of 96%.
- the methanol permeation amount of this membrane electrode composite was 5.4 / ⁇ ⁇ « ⁇ 2 ⁇ .
- the output in the noisy evaluation was 42 mWZcm 2 .
- the methanol permeation amount of this membrane electrode assembly was 3.8 molZcm 2 Z min.
- the output of passive evaluation exhibited 35m WZcm 2.
- these electrodes with the interface resistance reducing composition were laminated so that the interface resistance reducing composition was on the electrolyte membrane B side, and heated at 100 ° C for 1 minute at a pressure of 5 MPa. After pressing, the membrane electrode assembly is immersed in 50 ml of pure water for 30 minutes and remains in the interface resistance reducing composition! / The plasticizer was extracted and washed to produce a membrane electrode assembly.
- the voltage holding ratio of the membrane electrode composite was 0.23V at the initial voltage and 0.22V after 100 hours of constant current power generation, showing excellent durability of 96%.
- these electrodes with the interfacial resistance reducing composition were laminated so that the interfacial resistance reducing composition was on the electrolyte membrane A side, and heated at 100 ° C for 1 minute at a pressure of 5 MPa.
- the membrane electrode assembly was obtained by pressing. After pressing, the membrane electrode assembly was immersed in 50 ml of pure water for 30 minutes, and the plasticizer remaining in the interface resistance reducing composition was extracted and washed to prepare a membrane electrode assembly.
- the initial voltage was 0.25 V
- the voltage after 100 hours constant current power generation was 0.24 V
- the durability was 96%.
- the methanol permeation amount of this membrane electrode assembly was 5.0 ⁇ mol Zcm 2 Z min.
- the output of a passive evaluation showed 42mWZcm 2.
- the method for producing a membrane electrode assembly of the present invention can be applied to the production of membrane electrode assemblies of various electrochemical devices (for example, fuel cells, water electrolysis devices, black-hole alkaline electrolysis devices, etc.). Among these devices, it is suitable for a fuel cell, and particularly suitable for a fuel cell using hydrogen or methanol aqueous solution as fuel.
- various electrochemical devices for example, fuel cells, water electrolysis devices, black-hole alkaline electrolysis devices, etc.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Fuel Cell (AREA)
- Inert Electrodes (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP05809174A EP1858096B1 (en) | 2004-12-07 | 2005-11-24 | Film electrode composite element and production method therefor, and fuel cell |
US11/721,143 US7838164B2 (en) | 2004-12-07 | 2005-11-24 | Film electrode composite element and production method therefor, and fuel cell |
AT05809174T ATE533200T1 (de) | 2004-12-07 | 2005-11-24 | Zusammengesetztes filmelektrodenelement und herstellungsverfahren dafür und brennstoffzelle |
CA2590317A CA2590317C (en) | 2004-12-07 | 2005-11-24 | Membrane electrode assembly and method of producing the same and fuel cell |
KR1020077012689A KR101244565B1 (ko) | 2004-12-07 | 2005-11-24 | 막 전극 복합체의 제조 방법, 및 연료 전지 |
JP2006547802A JP5176321B2 (ja) | 2004-12-07 | 2005-11-24 | 膜電極複合体およびその製造方法、ならびに燃料電池 |
US12/833,760 US8278004B2 (en) | 2004-12-07 | 2010-07-09 | Membrane electrode assembly and method of producing the same and fuel cell |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004353914 | 2004-12-07 | ||
JP2004-353914 | 2004-12-07 | ||
JP2005-253178 | 2005-09-01 | ||
JP2005253178 | 2005-09-01 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/721,143 A-371-Of-International US7838164B2 (en) | 2004-12-07 | 2005-11-24 | Film electrode composite element and production method therefor, and fuel cell |
US12/833,760 Continuation US8278004B2 (en) | 2004-12-07 | 2010-07-09 | Membrane electrode assembly and method of producing the same and fuel cell |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006061993A1 true WO2006061993A1 (ja) | 2006-06-15 |
Family
ID=36577824
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2005/021507 WO2006061993A1 (ja) | 2004-12-07 | 2005-11-24 | 膜電極複合体およびその製造方法、ならびに燃料電池 |
Country Status (8)
Country | Link |
---|---|
US (2) | US7838164B2 (ja) |
EP (2) | EP2424019B1 (ja) |
JP (1) | JP5176321B2 (ja) |
KR (1) | KR101244565B1 (ja) |
AT (1) | ATE533200T1 (ja) |
CA (1) | CA2590317C (ja) |
TW (1) | TWI400832B (ja) |
WO (1) | WO2006061993A1 (ja) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008533269A (ja) * | 2005-03-16 | 2008-08-21 | インスティトゥート ナスィオナル ポリテクニク ド グルノーブル | 酸性イオン基を有する熱可塑性重合体の押出成形 |
JP2008537562A (ja) * | 2005-03-16 | 2008-09-18 | インスティトゥート ナスィオナル ポリテクニク ド グルノーブル | アルカリ性イオン基を有する熱可塑性重合体を押出すことを含む膜の製造方法 |
WO2009110052A1 (ja) * | 2008-03-03 | 2009-09-11 | 東洋紡績株式会社 | 高分子電解質膜とその用途及び高分子電解質膜の製造方法 |
JP2009245934A (ja) * | 2008-03-10 | 2009-10-22 | Toray Ind Inc | 電解質膜の製造方法 |
JP2016050779A (ja) * | 2014-08-28 | 2016-04-11 | 日産自動車株式会社 | 電極の評価方法 |
JP6432703B1 (ja) * | 2018-01-31 | 2018-12-05 | 凸版印刷株式会社 | 固体高分子形燃料電池用膜電極接合体、固体高分子形燃料電池及び固体高分子形燃料電池用膜電極接合体の製造方法 |
WO2019151310A1 (ja) * | 2018-01-31 | 2019-08-08 | 凸版印刷株式会社 | 固体高分子形燃料電池用膜電極接合体及び固体高分子形燃料電池 |
JP2020091973A (ja) * | 2018-12-04 | 2020-06-11 | 凸版印刷株式会社 | 固体高分子形燃料電池用膜電極接合体及び固体高分子形燃料電池 |
WO2022065591A1 (ko) * | 2020-09-23 | 2022-03-31 | 비나텍주식회사 | 전극 코팅층 형성을 위한 전극 슬러리 및 이를 이용한 연료전지용 막-전극접합체 제조 방법 |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7950221B2 (en) * | 2003-04-25 | 2011-05-31 | Catelectric Corp. | Methods and apparatus for controlling catalytic processes, including catalyst regeneration and soot elimination |
US20090101516A1 (en) * | 2007-09-20 | 2009-04-23 | The University Of Connecticut | Methods and apparatus for the synthesis of useful compounds |
US8617767B2 (en) * | 2008-04-24 | 2013-12-31 | Ird Fuel Cells A/S | Methods and systems for determining and controlling fuel concentrations in fuel cells |
WO2009139852A1 (en) * | 2008-05-12 | 2009-11-19 | Catelectric Corp. | Methods and apparatus for controlling catalytic processes, including the deposition of carbon based particles |
KR101041237B1 (ko) * | 2008-12-31 | 2011-06-14 | 두산중공업 주식회사 | 용융탄산염 연료전지의 제조방법 |
CN101734940B (zh) * | 2009-11-20 | 2012-07-25 | 中南大学 | 基于压差法快速cvi涂层的炭纸性能改善方法和装置 |
CN103328204B (zh) | 2010-10-27 | 2016-10-26 | 范德比尔特大学 | 纳米纤维电极及其制备方法 |
US20130157167A1 (en) * | 2011-12-20 | 2013-06-20 | GM Global Technology Operations LLC | Alternate material for electrode topcoat |
US8906572B2 (en) | 2012-11-30 | 2014-12-09 | General Electric Company | Polymer-electrolyte membrane, electrochemical fuel cell, and related method |
WO2015102618A1 (en) * | 2013-12-31 | 2015-07-09 | Rutgers, The State University Of New Jersey | Nickel phosphides electrocatalysts for hydrogen evolution and oxidation reactions |
JP6311319B2 (ja) * | 2014-01-14 | 2018-04-18 | 大日本印刷株式会社 | 樹脂組成物、リフレクター、リフレクター付きリードフレーム、及び半導体発光装置 |
US10361456B2 (en) | 2014-09-26 | 2019-07-23 | Samsung Electronics Co., Ltd. | Electrolyte, method of preparing the electrolyte, and secondary battery including the electrolyte |
EP3282512B1 (en) * | 2015-04-08 | 2023-05-03 | LG Chem, Ltd. | Polymer electrolyte membrane, electrochemical cell and flow cell comprising same, method for manufacturing polymer electrolyte membrane, and flow cell electrolyte |
JP7113232B2 (ja) * | 2017-02-23 | 2022-08-05 | パナソニックIpマネジメント株式会社 | 膜電極接合体および燃料電池 |
US20220246945A1 (en) * | 2019-12-10 | 2022-08-04 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Fibrous Electrode Material, Preparation and Application Thereof |
CN113314748B (zh) * | 2021-05-31 | 2022-09-02 | 安徽中能元隽氢能科技股份有限公司 | 一种基于表面改性聚合物骨架的增强型质子交换膜的制备方法 |
WO2024006758A2 (en) * | 2022-06-27 | 2024-01-04 | The Regents Of The University Of California | Li-ion-conducting polymer and polymer-ceramic electrolytes for solid state batteries |
DE102022212497A1 (de) | 2022-11-23 | 2024-05-23 | Robert Bosch Gesellschaft mit beschränkter Haftung | Konditionierungsverfahren und Konditionierungsvorrichtung zum Konditionieren einer Membranelektrodeneinheit einer Brennstoffzelle |
Citations (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02305881A (ja) * | 1989-05-20 | 1990-12-19 | Nitta Gelatin Inc | 反応性ホットメルト接着剤 |
JPH04255776A (ja) * | 1991-02-07 | 1992-09-10 | Hitachi Chem Co Ltd | 紫外線硬化型接着剤シートその製造法その製造法に用いる装置その接着剤シートを用いて配線板用基板を製造する方法およびその接着剤シートを用いて配線板を製造する方法 |
JPH07220741A (ja) * | 1994-01-28 | 1995-08-18 | Asahi Glass Co Ltd | 固体高分子型燃料電池用電極・膜接合体の製造方法 |
JPH08148152A (ja) * | 1994-11-17 | 1996-06-07 | Tokyo Gas Co Ltd | 固体高分子型燃料電池用電極及びその製造方法 |
JPH09223503A (ja) * | 1996-02-14 | 1997-08-26 | Tanaka Kikinzoku Kogyo Kk | 高分子固体電解質型燃料電池用電極の製造方法 |
JPH09274924A (ja) * | 1996-02-05 | 1997-10-21 | Honda Motor Co Ltd | 燃料電池用電極構造体の製造方法 |
JPH11339824A (ja) * | 1998-05-22 | 1999-12-10 | Asahi Glass Co Ltd | 固体高分子電解質型の燃料電池用電極−膜接合体の製造方法 |
JP2000285932A (ja) * | 1999-03-31 | 2000-10-13 | Asahi Glass Co Ltd | 固体高分子型燃料電池用電極・膜接合体の製造方法 |
JP2001110428A (ja) * | 1999-10-08 | 2001-04-20 | Matsushita Electric Ind Co Ltd | 高分子電解質型燃料電池 |
FR2810794A1 (fr) | 2000-06-26 | 2001-12-28 | Sorapec | Association d'electrodes et de membrane comportant des conducteurs protoniques |
JP2002216801A (ja) * | 2001-01-19 | 2002-08-02 | Honda Motor Co Ltd | 高分子電解質型燃料電池及びその製造方法 |
JP2004006306A (ja) * | 2002-04-17 | 2004-01-08 | Nec Corp | 燃料電池、燃料電池用電極およびそれらの製造方法 |
WO2004051776A1 (ja) | 2002-12-02 | 2004-06-17 | Sanyo Electric Co.,Ltd. | 固体高分子電解質膜、当該膜を用いた固体高分子型燃料電池、およびその製造方法 |
JP2004185930A (ja) * | 2002-12-02 | 2004-07-02 | Sanyo Electric Co Ltd | 固体高分子型燃料電池の製造方法 |
JP2004224953A (ja) * | 2003-01-24 | 2004-08-12 | Toyobo Co Ltd | イオン交換膜およびその製造方法 |
JP2004253267A (ja) * | 2003-02-20 | 2004-09-09 | Jsr Corp | 電解膜−電極基板複合体の製造方法 |
WO2004091027A1 (ja) | 2003-04-09 | 2004-10-21 | Nec Corporation | 燃料電池およびその製造方法 |
JP2005129295A (ja) * | 2003-10-22 | 2005-05-19 | Honda Motor Co Ltd | 燃料電池用電極−膜接合体の製造方法 |
Family Cites Families (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2810794A (en) * | 1954-05-19 | 1957-10-22 | Gen Motors Corp | Headlight control switch |
JPS59209278A (ja) | 1983-05-13 | 1984-11-27 | Hitachi Ltd | 燃料電池 |
JP3264920B2 (ja) | 1990-09-21 | 2002-03-11 | 松下電器産業株式会社 | 液体燃料電池 |
US5403675A (en) | 1993-04-09 | 1995-04-04 | Maxdem, Incorporated | Sulfonated polymers for solid polymer electrolytes |
JP4132168B2 (ja) | 1998-01-13 | 2008-08-13 | ポップリベット・ファスナー株式会社 | パイプ等の長尺物の保持具 |
US7361729B2 (en) | 2000-09-20 | 2008-04-22 | Virginia Tech Intellectual Properties, Inc. | Ion-conducting sulfonated polymeric materials |
CA2429104C (en) * | 2000-11-09 | 2010-12-21 | Trustees Of The University Of Pennsylvania | The use of sulfur-containing fuels for direct oxidation fuel cells |
DE10201692A1 (de) * | 2001-01-19 | 2002-09-05 | Honda Motor Co Ltd | Membranelektrodenanordnung und Verfahren zu deren Herstellung und eine Polymerelektrolytbrennstoffzelle, die eine derartige Membranelektrodenanordnung umfasst |
US6689501B2 (en) * | 2001-05-25 | 2004-02-10 | Ballard Power Systems Inc. | Composite ion exchange membrane for use in a fuel cell |
DE10129458A1 (de) * | 2001-06-19 | 2003-01-02 | Celanese Ventures Gmbh | Verbesserte Polymerfolien auf Basis von Polyazolen |
DE60236281D1 (de) * | 2001-06-26 | 2010-06-17 | Victrex Mfg Ltd | Herstellungsverfahren für membranen |
US6544534B2 (en) * | 2001-08-21 | 2003-04-08 | Janice K. Malmgren | Conditioner that provides skin like an angel |
JP2003109606A (ja) * | 2001-09-28 | 2003-04-11 | Matsushita Electric Ind Co Ltd | 高分子電解質型燃料電池とその製造方法 |
JP2003282075A (ja) * | 2002-03-26 | 2003-10-03 | Matsushita Electric Ind Co Ltd | 燃料電池とその製造方法 |
JP2003297373A (ja) * | 2002-04-08 | 2003-10-17 | Matsushita Electric Ind Co Ltd | 触媒層用塗料とこれを用いた電解質膜電極接合体の製造方法 |
JP3696171B2 (ja) * | 2002-04-16 | 2005-09-14 | 株式会社東芝 | 直接型液体燃料電池発電装置の検査方法、検査装置、及び直接型液体燃料電池発電装置 |
JP3608564B2 (ja) * | 2002-04-17 | 2005-01-12 | 日本電気株式会社 | 燃料電池およびその製造方法 |
US7700211B2 (en) * | 2002-04-17 | 2010-04-20 | Nec Corporation | Fuel cell, fuel cell electrode and method for fabricating the same |
WO2004004037A1 (ja) * | 2002-06-28 | 2004-01-08 | Sumitomo Chemical Company, Limited | 高分子積層膜、その製造方法およびその用途 |
JP4649094B2 (ja) * | 2003-03-07 | 2011-03-09 | 旭化成イーマテリアルズ株式会社 | 燃料電池用膜電極接合体の製造方法 |
JP2004296435A (ja) * | 2003-03-13 | 2004-10-21 | Toray Ind Inc | 電極触媒層およびその製造方法ならびにそれを用いた固体高分子型燃料電池 |
JP2004296278A (ja) * | 2003-03-27 | 2004-10-21 | Ube Ind Ltd | 小型燃料電池および電解質膜 |
JPWO2004090015A1 (ja) * | 2003-04-07 | 2006-07-06 | 三井化学株式会社 | 架橋性イオン伝導性樹脂、並びにそれを用いてなるイオン伝導性高分子膜、結着剤及び燃料電池 |
JP4255776B2 (ja) | 2003-08-12 | 2009-04-15 | 株式会社小森コーポレーション | 折機のドラグローラ装置 |
KR100684734B1 (ko) * | 2005-06-28 | 2007-02-20 | 삼성에스디아이 주식회사 | 연료 전지용 고분자 전해질 막, 이의 제조 방법 및 이를 포함하는 연료 전지 장치 |
-
2005
- 2005-11-24 US US11/721,143 patent/US7838164B2/en active Active
- 2005-11-24 AT AT05809174T patent/ATE533200T1/de active
- 2005-11-24 JP JP2006547802A patent/JP5176321B2/ja active Active
- 2005-11-24 EP EP11008895.2A patent/EP2424019B1/en active Active
- 2005-11-24 CA CA2590317A patent/CA2590317C/en active Active
- 2005-11-24 EP EP05809174A patent/EP1858096B1/en active Active
- 2005-11-24 WO PCT/JP2005/021507 patent/WO2006061993A1/ja active Application Filing
- 2005-11-24 KR KR1020077012689A patent/KR101244565B1/ko active IP Right Grant
- 2005-12-01 TW TW094142217A patent/TWI400832B/zh not_active IP Right Cessation
-
2010
- 2010-07-09 US US12/833,760 patent/US8278004B2/en active Active
Patent Citations (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02305881A (ja) * | 1989-05-20 | 1990-12-19 | Nitta Gelatin Inc | 反応性ホットメルト接着剤 |
JPH04255776A (ja) * | 1991-02-07 | 1992-09-10 | Hitachi Chem Co Ltd | 紫外線硬化型接着剤シートその製造法その製造法に用いる装置その接着剤シートを用いて配線板用基板を製造する方法およびその接着剤シートを用いて配線板を製造する方法 |
JPH07220741A (ja) * | 1994-01-28 | 1995-08-18 | Asahi Glass Co Ltd | 固体高分子型燃料電池用電極・膜接合体の製造方法 |
JPH08148152A (ja) * | 1994-11-17 | 1996-06-07 | Tokyo Gas Co Ltd | 固体高分子型燃料電池用電極及びその製造方法 |
JPH09274924A (ja) * | 1996-02-05 | 1997-10-21 | Honda Motor Co Ltd | 燃料電池用電極構造体の製造方法 |
JPH09223503A (ja) * | 1996-02-14 | 1997-08-26 | Tanaka Kikinzoku Kogyo Kk | 高分子固体電解質型燃料電池用電極の製造方法 |
JPH11339824A (ja) * | 1998-05-22 | 1999-12-10 | Asahi Glass Co Ltd | 固体高分子電解質型の燃料電池用電極−膜接合体の製造方法 |
JP2000285932A (ja) * | 1999-03-31 | 2000-10-13 | Asahi Glass Co Ltd | 固体高分子型燃料電池用電極・膜接合体の製造方法 |
JP2001110428A (ja) * | 1999-10-08 | 2001-04-20 | Matsushita Electric Ind Co Ltd | 高分子電解質型燃料電池 |
FR2810794A1 (fr) | 2000-06-26 | 2001-12-28 | Sorapec | Association d'electrodes et de membrane comportant des conducteurs protoniques |
JP2002216801A (ja) * | 2001-01-19 | 2002-08-02 | Honda Motor Co Ltd | 高分子電解質型燃料電池及びその製造方法 |
JP2004006306A (ja) * | 2002-04-17 | 2004-01-08 | Nec Corp | 燃料電池、燃料電池用電極およびそれらの製造方法 |
WO2004051776A1 (ja) | 2002-12-02 | 2004-06-17 | Sanyo Electric Co.,Ltd. | 固体高分子電解質膜、当該膜を用いた固体高分子型燃料電池、およびその製造方法 |
JP2004185930A (ja) * | 2002-12-02 | 2004-07-02 | Sanyo Electric Co Ltd | 固体高分子型燃料電池の製造方法 |
JP2004224953A (ja) * | 2003-01-24 | 2004-08-12 | Toyobo Co Ltd | イオン交換膜およびその製造方法 |
JP2004253267A (ja) * | 2003-02-20 | 2004-09-09 | Jsr Corp | 電解膜−電極基板複合体の製造方法 |
WO2004091027A1 (ja) | 2003-04-09 | 2004-10-21 | Nec Corporation | 燃料電池およびその製造方法 |
JP2005129295A (ja) * | 2003-10-22 | 2005-05-19 | Honda Motor Co Ltd | 燃料電池用電極−膜接合体の製造方法 |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008533269A (ja) * | 2005-03-16 | 2008-08-21 | インスティトゥート ナスィオナル ポリテクニク ド グルノーブル | 酸性イオン基を有する熱可塑性重合体の押出成形 |
JP2008537562A (ja) * | 2005-03-16 | 2008-09-18 | インスティトゥート ナスィオナル ポリテクニク ド グルノーブル | アルカリ性イオン基を有する熱可塑性重合体を押出すことを含む膜の製造方法 |
WO2009110052A1 (ja) * | 2008-03-03 | 2009-09-11 | 東洋紡績株式会社 | 高分子電解質膜とその用途及び高分子電解質膜の製造方法 |
JP2009245934A (ja) * | 2008-03-10 | 2009-10-22 | Toray Ind Inc | 電解質膜の製造方法 |
JP2016050779A (ja) * | 2014-08-28 | 2016-04-11 | 日産自動車株式会社 | 電極の評価方法 |
JP6432703B1 (ja) * | 2018-01-31 | 2018-12-05 | 凸版印刷株式会社 | 固体高分子形燃料電池用膜電極接合体、固体高分子形燃料電池及び固体高分子形燃料電池用膜電極接合体の製造方法 |
WO2019151310A1 (ja) * | 2018-01-31 | 2019-08-08 | 凸版印刷株式会社 | 固体高分子形燃料電池用膜電極接合体及び固体高分子形燃料電池 |
JP2019133906A (ja) * | 2018-01-31 | 2019-08-08 | 凸版印刷株式会社 | 固体高分子形燃料電池用膜電極接合体、固体高分子形燃料電池及び固体高分子形燃料電池用膜電極接合体の製造方法 |
JP2020091973A (ja) * | 2018-12-04 | 2020-06-11 | 凸版印刷株式会社 | 固体高分子形燃料電池用膜電極接合体及び固体高分子形燃料電池 |
JP7256359B2 (ja) | 2018-12-04 | 2023-04-12 | 凸版印刷株式会社 | 固体高分子形燃料電池用膜電極接合体及び固体高分子形燃料電池 |
WO2022065591A1 (ko) * | 2020-09-23 | 2022-03-31 | 비나텍주식회사 | 전극 코팅층 형성을 위한 전극 슬러리 및 이를 이용한 연료전지용 막-전극접합체 제조 방법 |
Also Published As
Publication number | Publication date |
---|---|
EP1858096A1 (en) | 2007-11-21 |
KR20070085786A (ko) | 2007-08-27 |
US20100015493A1 (en) | 2010-01-21 |
EP1858096B1 (en) | 2011-11-09 |
EP1858096A4 (en) | 2010-03-10 |
KR101244565B1 (ko) | 2013-03-20 |
JPWO2006061993A1 (ja) | 2008-06-05 |
JP5176321B2 (ja) | 2013-04-03 |
US8278004B2 (en) | 2012-10-02 |
CA2590317A1 (en) | 2006-06-15 |
EP2424019A1 (en) | 2012-02-29 |
EP2424019B1 (en) | 2013-06-12 |
US7838164B2 (en) | 2010-11-23 |
TW200629632A (en) | 2006-08-16 |
ATE533200T1 (de) | 2011-11-15 |
TWI400832B (zh) | 2013-07-01 |
CA2590317C (en) | 2013-05-21 |
US20100291460A1 (en) | 2010-11-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5176321B2 (ja) | 膜電極複合体およびその製造方法、ならびに燃料電池 | |
US7824786B2 (en) | Membrane electrode complex and solid type fuel cell using it | |
KR20110005774A (ko) | 고체 고분자형 연료 전지용 막전극 접합체 및 고체 고분자형 연료 전지 | |
JP5195286B2 (ja) | 固体高分子形燃料電池用膜電極接合体の製造方法 | |
CN100559641C (zh) | 膜电极复合体及其制造方法、和燃料电池 | |
JP2005353581A (ja) | 電解質膜および膜電極複合体ならびに高分子電解質型燃料電池 | |
JP2006253124A (ja) | 電解質膜用支持体、それを用いた高分子電解質複合膜の処理方法、およびその処理が施された高分子電解質複合膜、ならびにそれを用いた燃料電池。 | |
Gubler et al. | A proton-conducting polymer membrane as solid electrolyte–function and required properties | |
JP5347251B2 (ja) | 膜電極複合体の製造方法 | |
JP2007214112A (ja) | 膜電極複合体 | |
JP2008234968A (ja) | 膜電極複合体ならびにそれの製造方法および高分子電解質型燃料電池 | |
KR101630212B1 (ko) | Pai-ptm 부직포에 탄화수소계 고분자 전해질을 함침시켜 제조한 복합막 및 이의 용도 | |
JP2007073324A (ja) | 膜電極複合体ならびにそれの製造方法および高分子電解質型燃料電池ならびにそれの製造方法 | |
JP2006202598A (ja) | 燃料電池用電極および燃料電池 | |
JP2015228292A (ja) | 固体高分子電解質膜、膜−電極接合体、燃料電池、水電解セルおよび水電解装置 | |
JP2009049004A (ja) | 液体供給型燃料電池の製造方法 | |
JP5309803B2 (ja) | 水素燃料電池用膜電極複合体 | |
JP5504552B2 (ja) | 非対称型電解質膜ならびにそれを用いた膜電極複合体および高分子電解質型燃料電池 | |
JP5017831B2 (ja) | 非対称型電解質膜ならびにそれを用いた膜電極複合体および高分子電解質型燃料電池 | |
JP2007141832A (ja) | 膜電極複合体ならびにそれの製造方法および高分子電解質型燃料電池ならびにそれの製造方法 | |
JP2006236986A (ja) | 電極およびその製造方法およびその用途 | |
JP2008258155A (ja) | 膜電極複合体およびその製造方法ならびに高分子電解質型燃料電池 | |
JP2011230387A (ja) | 積層体 | |
JP2009081133A (ja) | 膜電極複合体およびその製造方法ならびにそれを用いた高分子電解質型燃料電池 | |
KR20150074305A (ko) | Pan 부직포 지지체에 탄화수소계 전해질을 함침시켜 제조한 복합막 및 이의 용도 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KN KP KR KZ LC LK LR LS LT LU LV LY MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU LV MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2006547802 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2590317 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020077012689 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 200580042080.6 Country of ref document: CN |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2005809174 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 2005809174 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 11721143 Country of ref document: US |